C urrently, technology is looking for smaller scale, ordered materials with well-defined properties. Nanophase materials are, therefore, being manufactured in increasing numbers. 1Ϫ3 Nature is also a prolific producer of nanophase materials. A typical example of this is the microorganism assisted, or biogenic, oxidation of water-soluble metal ions into insoluble oxides. 4 Indeed this process has been taking place for millions of years leaving its signature all around: in the sediments on the ocean floor and in the soil on land. Nature's evident success is inspiring and scientists are trying to employ its tools for applications including manufacturing of magnetic nanoparticles 5 and capturing of contaminant metal ions. 6Ϫ8 Thus understanding the way living microorganisms produce materials, in particular nanophase metal oxides, is becoming important not only for the advance of today's technology but also for remediating some of its unwanted consequences such as metal pollution.One of the most important prerequisites to understanding a physicochemical process, such as the formation of a nanophase material, is the knowledge of the atomic-scale structure of its product. Recently, good progress has been made in determining the structure of synthetic (i.e., man-made) nanophase materials by employing total X-ray diffraction (XRD) involving a combination of high-energy XRD and atomic pair distribution function (PDF) analysis. 9Ϫ11 This nontraditional approach has also been applied to nanophase materials of geological interest, such as ores. 12 The approach can also be applied to materials freshly produced by living microorganisms. As an example we consider MnO x produced by bacteria and fungi. These biogenic materials show a length of structural coherence of about 2Ϫ3 nm only and, in this sense, are in a nanophase state. Nevertheless, their atomic-scale structure is periodic and can be described in simple crystallographic terms. Surprisingly the crystal structures of fungal and bacterial MnO x turn out to be substantially different indicating that biogenic materials are inherently structurally diverse.Manganese oxides are ubiquitous in nature 13 and have been used by mankind for many thousands of yearsOfirst as pigments and today as catalysts and battery materials. This has generated a long-lasting interest in their genesis. Several studies on MnO x produced by microorganisms have been carried out but no complete structural determination has yet been performed. The studies have only suggested that bacterial MnO x is likely to possess a layered-type structure of the type found in the mineral birnessite. 14,15 Even less is known about fungal MnO x . 16,17 *Address correspondence to petkov@phy.cmich.edu. As such, they are difficult to characterize structurally. In this report, we demonstrate how high-energy X-ray diffraction and atomic pair distribution function analysis can be used to determine the atomic-scale structures of MnO x produced by bacteria and fungi. These structures are well-defined, periodic, and species-sp...